TWI777979B - Halftone Phase Shift Blank Mask and Halftone Phase Shift Mask - Google Patents

Abstract

The solution of the present invention is a halftone phase shift blank mask, which is characterized in that the halftone phase shift film is composed of a silicon-based material containing transition metals, silicon and nitrogen as essential components, and may contain oxygen as an optional component. At least one layer is composed of a transition metal content of 3 atomic % or less, a total content of silicon, nitrogen and oxygen of 90 atomic % or more, a silicon content of 30 to 70 atomic %, and a total of nitrogen and oxygen content. A layer composed of a silicon-based material with a rate of 30 to 60 atomic % and an oxygen content of 30 atomic % or less, and a sheet resistance of 10 ¹³ Ω/□ or less. The effect of the present invention is to provide a film with less pattern size variation and deterioration with respect to irradiation of light with a wavelength of 200 nm or less, good chemical resistance, and improved processing compared with a film of a silicon-based material that does not contain a transition metal. Halftone Phase Shift Blank Mask and Halftone Phase Shift Mask of Sexual Halftone Phase Shift Film.

Description

Halftone Phase Shift Blank Mask and Halftone Phase Shift Mask

[0001] The present invention relates to a halftone phase shift blank mask and a halftone phase shift mask used in the manufacture of semiconductor integrated circuits and the like.

[0002] In the field of semiconductor technology, research and development for further miniaturization of patterns is progressing. Especially in recent years, along with the high integration of large-scale integrated circuits, the miniaturization of circuit patterns, the thinning of wiring patterns, and the miniaturization of contact hole patterns for forming interlayer wiring between components have gradually been carried out. Raise the demand for microfabrication technology. As a result, even in the field of manufacturing techniques for photomasks used in photolithography steps in microfabrication, techniques for forming finer and more accurate circuit patterns (mask patterns) are being developed. [0003] Generally, when a pattern is formed on a semiconductor substrate by photolithography, a reduced projection is performed. Therefore, the size of the pattern formed by the photomask becomes about 4 times the size of the pattern formed on the semiconductor substrate. In today's field of photolithography, the size of the circuit pattern drawn becomes much lower than the wavelength of the light used for exposure. Therefore, when the size of the circuit pattern is simply quadrupled and a mask pattern is formed, the original shape cannot be transferred to the resist film on the semiconductor substrate due to the influence of interference of light generated during exposure. result. [0004] Therefore, there are cases in which the above-mentioned effects of light interference and the like are reduced by making the pattern formed on the mask into a more complicated shape than the actual circuit pattern. As such a pattern shape, for example, there is a shape in which Optical Proximity Correction (OPC: Optical Proximity Correction) is performed on an actual circuit pattern. In addition, in order to meet the miniaturization and high precision of patterns, technologies such as anamorphic lighting, liquid immersion technology, resolution enhancement technology (RET: Resolution Enhancement Technology), and double exposure (Double patterning lithography) are also applied. [0005] As one of the RETs, the phase shift method is used. The phase shift method is a method in which a pattern of a film whose phase is reversed by about 180° is formed on a photomask, and the contrast is enhanced by the interference of light. One of the masks to apply this is the Halftone Phase Shift Mask. The halftone phase shift mask is formed on a substrate such as quartz, which is transparent to exposure light, to form a halftone phase shift film that inverts the phase by about 180° and has a transmittance that does not affect pattern formation. mask pattern. As a halftone phase shift mask, there has been proposed one having a halftone phase shift film composed of molybdenum silicide oxide (MoSiO) and molybdenum silicide nitride oxide (MoSiON) (Japanese Patent Laid-Open No. 7-140635 (Patent Document) 1)). In addition, in order to obtain a finer image by photolithography, and to use a shorter wavelength for the exposure light source, in the current most advanced practical processing steps, the exposure light source is shifted from KrF excimer laser light (248nm) to ArF excimer laser light (193 nm). However, it was found that by using the higher energy ArF excimer laser, mask damage not observed with the KrF excimer laser occurred. One of them is that there is a problem that foreign matter-like growth defects are generated on the photomask when the photomask is used continuously. This growth defect is called haze, and although the cause was initially thought to be the growth of ammonium sulfate crystals on the surface of the mask pattern, it is now gradually thought to be related to organic matter. [0007] As a countermeasure against the haze problem, for example, in Japanese Patent Laid-Open No. 2008-276002 (Patent Document 2), it is shown that the growth defects generated when the mask is irradiated with ArF excimer laser light for a long time, The reticle is cleaned at a predetermined stage, and the reticle can be used continuously. In addition, it has been reported that with the increase of the exposure irradiation amount of ArF excimer laser light in pattern transfer, damage different from haze is generated in the mask, and the pattern size of the mask is changed in response to the accumulated irradiation energy ( Thomas Faure et al., "Characterization of binary mask and attenuated phase shift mask blanks for 32nm mask fabrication", Proc. Of SPIE, vol. 7122, pp712209-1～712209-12 (non-patent literature 1)). In this case, when ArF excimer laser light is irradiated for a long time, the cumulative irradiation energy increases, and since a layer made of a substance considered to be an oxide of the pattern material grows outside the film pattern, there is a problem that the pattern width is changed. In addition, it is considered that the mask that has suffered this damage has been shown to be unable to be cleaned by the ammonia water/hydrogen peroxide water used for the removal of the aforementioned haze, or by the cleaning by sulfuric acid/hydrogen peroxide water. Reply, for other reasons entirely. Furthermore, according to the above-mentioned report of Thomas Faure et al. (Non-Patent Document 1), it is pointed out that pattern exposure in circuits is a useful masking technique for extending the depth of focus, that is, halftone phase-shift masking, especially due to the above-mentioned ArF Deterioration due to pattern size variation (hereinafter, referred to as pattern size variation degradation) accompanying the modification of transition metal-silicon-based material films such as MoSi-based material films by irradiation with excimer laser light is large. Therefore, in order to use an expensive photomask for a long period of time, it is necessary to take measures against the variation and deterioration of the pattern size due to the irradiation of ArF excimer laser light. [Prior Art Document] [Patent Document] [0010] [Patent Document 1] Japanese Patent Laid-Open No. 7-140635 [Patent Document 2] Japanese Patent Laid-Open No. 2008-276002 [Patent Document 3] Japanese Patent Laid-Open No. 2004-133029 Publication [Patent Document 4] Japanese Patent Laid-Open No. 2007-33469 [Patent Document 5] Japanese Patent Laid-Open No. 2007-233179 [Patent Document 6] Japanese Patent Laid-Open No. 2007-241065 [Non-Patent Document] [0011] [Non-Patent Document 6] Patent Document 1] Thomas Faure et al., “Characterization of binary mask and attenuated phase shift mask blanks for 32nm mask fabrication”, Proc. Of SPIE, vol. 7122, pp712209-1～712209-12

[Problems to be Solved by the Invention] [0012] When the blank photomask is used in the photomask manufacturing process, when there is foreign matter on the blank photomask, the foreign matter becomes the cause of pattern defects. In order to remove such foreign matter, the blank photomask There are multiple washes during the reticle manufacturing process. Furthermore, when the photomask is used in the photolithography step, even if the photomask itself has no pattern defects, in the photolithography step, when foreign matter is attached to the photomask, it is used in the patterned semiconductor substrate. , it will cause poor pattern transfer, so the mask is also repeatedly cleaned. [0013] In almost all cases, chemical cleaning is performed by a mixture of sulfuric acid hydrogen peroxide, ozone water, ammonia hydrogen peroxide, etc. Here, the sulfuric acid-hydrogen peroxide water mixture is a detergent with strong oxidizing effect obtained by mixing sulfuric acid and hydrogen peroxide water, and the ozone water is one that dissolves ozone into water, which is used as an alternative to the sulfuric acid-hydrogen peroxide water mixture. In particular, the mixture of ammonia and hydrogen peroxide is a detergent obtained by mixing ammonia water and hydrogen peroxide water. When the organic foreign matter attached to the surface is immersed in the mixture of ammonia and hydrogen peroxide, the dissolution of ammonia and the oxidation of hydrogen peroxide are used. As a result, the organic foreign matter is detached and separated from the surface, thereby cleaning. The chemical cleaning caused by such a medicinal solution is necessary to remove the particles or contaminants attached to the blank mask or the mask, and there may be a risk to the blank mask or the mask. There is a risk of damage to optical films such as a halftone phase shift film provided. For example, by chemical cleaning as described above, the surface of the optical film may be degraded, and the optical properties that it should have originally may be changed. Due to the chemical cleaning of the blank mask or the mask, it is necessary to repeat the implementation. In addition, it is necessary to suppress the characteristic change (for example, retardation change) of the optical film generated in each cleaning step as low as possible. In addition, the pattern size variation and deterioration caused by the irradiation of short-wavelength light such as ArF excimer laser light, such as the report of above-mentioned Thomas Faure etc. (Non-Patent Document 1), is clear that the light is irradiated in a dry air environment. If it is difficult to occur in the case of , as a new measure to prevent the pattern size variation and deterioration, a method of exposure in dry air is considered. However, in addition to the additional device required for the regulation by the dry air environment, anti-static measures are also required, resulting in an increase in cost. Therefore, in a common environment (for example, about 45% humidity) without complete removal of humidity, long-term exposure becomes necessary. [0016] In the photomask used for photolithography using ArF excimer laser light as a light source, a transition metal silicon-based material, usually a silicon-based material containing molybdenum, is used in the halftone phase shift film. The main constituent elements of this transition metal-silicon-based material are transition metals and silicon, and some contain nitrogen and/or oxygen as light elements (for example, Japanese Patent Laid-Open No. 7-140635 (Patent Document 1)). As the transition metal, molybdenum, zirconium, tantalum, tungsten, titanium, etc. are used. In particular, molybdenum is generally used (for example, Japanese Patent Laid-Open No. 7-140635 (Patent Document 1)). 2 In the case of transition metal (Japanese Patent Laid-Open No. 2004-133029 (Patent Document 3)). In addition, transition metal silicon-based materials are also used in the light-shielding film, and silicon-based materials containing molybdenum are generally used. However, when a photomask using such a transition metal-silicon-based material is irradiated with a large amount of high-energy light, the pattern size variation and deterioration caused by the irradiation of the high-energy light are large, resulting in a shorter service life of the photomask than required. . [0017] By irradiating the mask pattern of the halftone phase shift mask with short wavelength light such as ArF excimer laser light, the pattern size variation and deterioration of the line width change of the mask pattern used for exposure are significant. question. The allowable limit of pattern width varies with the type of reticle pattern, especially the pattern rules that apply. In addition, although there are some changes, the exposure conditions can be corrected, and the exposure conditions of the exposure device can be set and used. The variation in the line width of the mask pattern needs to be about ±5 nm or less. However, when the variation of the pattern width is large, there is a possibility that the variation may be distributed within the mask surface. In addition, by further miniaturization, extremely fine auxiliary patterns of 100 nm or less are also formed on the mask. Therefore, due to the miniaturization of the patterns on these masks and the increase of the mask processing cost due to the complexity of the mask patterns, the variation and deterioration of the pattern size are extremely small, and the halftone phase shift mask of repeated exposure can be performed. A cover film becomes necessary. [0018] As such a requirement, a film of a silicon-based material that does not contain a transition metal, such as a film composed of silicon and nitrogen, or a film composed of silicon, nitrogen, and oxygen, can be cited. The film can improve chemical resistance, or degrade pattern size variation. However, such a film has a problem that the dry etching rate is slow and the workability is deteriorated. The present invention is accomplished in order to solve the above-mentioned problems, to provide a kind of short-wavelength light with high energy below 200 nm using ArF excimer laser, etc., when performing pattern exposure, even if the cumulative irradiation energy is much situation. It also suppresses the deterioration of the pattern size due to the change of the film quality of the photomask due to the irradiated light, has good chemical resistance, and has good processability. Halftone phase shift blank mask and halftone phase shift mask hood as the purpose. [MEANS TO SOLVE THE PROBLEM] [0020] The present inventors aimed at the development of a halftone phase shift film with little deterioration in the size variation of the pattern irradiated with ArF excimer laser light and good chemical resistance. Halftone phase shift films of silicon-based materials containing transition metals are studied for films composed of silicon and nitrogen or halftone phase shift films composed of silicon, nitrogen and oxygen that do not contain transition metals. However, in such a halftone phase shift film, although dry etching can be performed with a fluorine-based gas, the dry etching rate is slow and the workability is deteriorated. Here, the present inventors, as a result of diligent research in order to solve the above-mentioned problems, found that the halftone phase shift film can be transitioned by containing transition metal, silicon, and nitrogen as essential components, and may also contain oxygen as an optional component. The metal content is 3 atomic % or less, the total content of silicon, nitrogen and oxygen is 90 atomic % or more, the silicon content is 30 to 70 atomic %, and the total nitrogen and oxygen content is 30 to 60 atomic %, and the oxygen content is 30 atomic % or less of a silicon-based material, the pattern size is deteriorated when irradiated with light with a wavelength of 200 nm or less, or the chemical resistance is equivalent to that of a silicon-based material that does not contain transition metals. The fluorine-based gas dry etching has a fast etching rate, and can form a halftone phase-shift film with improved workability compared with silicon-based materials that do not contain transition metals, thereby completing the present invention. Accordingly, the present invention provides the following halftone phase shift blank mask and halftone phase shift mask. Claim 1: A halftone phase shift blank mask, which is composed of a single layer or a plurality of layers on a transparent substrate, the phase shift amount is 150-200°, and the transmittance is 3 for light with a wavelength of 200 nm or less. A halftone phase shift blank mask with a halftone phase shift film of ~30%, characterized in that the halftone phase shift film is a silicon-based material containing transition metals, silicon and nitrogen as essential components, and optionally oxygen as an optional component It is constituted, as a layer constituting the above-mentioned halftone phase shift film, at least one layer (A) is composed of a transition metal content of 3 atomic % or less, a total content of silicon, nitrogen and oxygen of 90 atomic % or more, The content of silicon is 30 to 70 atomic %, the total content of nitrogen and oxygen is 30 to 60 atomic %, and the oxygen content is 30 atomic % or less of a silicon-based material, and the sheet resistance is 10 ¹³ Ω The layer below /□. Claim 2: The halftone phase shift blank mask of claim 1, wherein the transition metal system includes molybdenum. Claim 3: The halftone phase shift blank mask according to claim 1 or 2, wherein the composition of a part or all of the above-mentioned (A) layer system constituent elements continuously changes in the thickness direction. Claim 4: The halftone phase shift blank mask according to any one of Claims 1 to 3, wherein the thickness of the phase shift film is 70 nm or less. Claim 5: The halftone phase shift blank mask according to any one of Claims 1 to 4, wherein the surface roughness RMS of the halftone phase shift film is 0.6 nm or less. Claim 6: The halftone phase shift blank mask according to any one of Claims 1 to 5, further comprising a single layer or a plurality of layers made of a material including chromium on the halftone phase shift film. The second layer of composition. Claim 7: The halftone phase-shift blank mask of claim 6, wherein the second layer is a light-shielding film, a combination of a light-shielding film and an anti-reflection film, or is used in the pattern formation of the above-mentioned halftone phase-shift film A processing aid film for hard masks. Claim 8: The halftone phase shift blank mask of claim 6, further comprising a third layer consisting of a single layer or a plurality of layers made of a material containing silicon on the second layer. Claim 9: The halftone phase-shift blank mask of claim 8, wherein the second layer is a light-shielding film, or a combination of a light-shielding film and an anti-reflection film, or in the pattern formation of the above-mentioned halftone phase-shift film Used as a processing aid film for a hard mask, the third layer is used as a processing aid film for the hard mask in the pattern formation of the second layer. Claim 10: The halftone phase-shift blank mask of claim 8, wherein the second layer is used as a hard mask in the patterning of the halftone phase-shift film, and the third layer in the image The third layer is a light-shielding film, or a combination of a light-shielding film and an antireflection film. Claim 11: The halftone phase shift blank mask of claim 8, further comprising a fourth layer consisting of a single layer or a plurality of layers made of a material including chromium on the third layer. Claim 12: The halftone phase shift blank mask of claim 11, wherein the second layer is used as a hard mask in the patterning of the halftone phase shift film, and the third layer is used as a hard mask in the patterning of the halftone phase shift film. The above-mentioned 3rd layer is a light-shielding film or a combination of a light-shielding film and an anti-reflection film, and the above-mentioned 4th layer is formed on the pattern of the above-mentioned 3rd layer and used as a hard mask Auxiliary film for the processing of the cover. Claim 13: A halftone phase shift mask, characterized by being formed by using the halftone phase shift blank mask according to any one of Claims 1 to 12. [Effects of the Invention] [0023] According to the present invention, it is possible to provide a kind of light with a wavelength of 200 nm or less, which has less pattern size variation and deterioration, and has good chemical resistance, and is compatible with silicon-based materials that do not contain transition metals. The halftone phase shift blank mask and the halftone phase shift mask of the halftone phase shift film with improved processability compared with the film. That is, the halftone phase shift film of the present invention has the same level of laser irradiation resistance and chemical resistance as the film containing silicon and nitrogen and does not contain transition metal materials, and the etching speed during fluorine-based dry etching is higher than Films of silicon and nitrogen materials that do not contain transition metals are faster and have excellent processability. In addition, the halftone phase shift film of the present invention has low sheet resistance and suppresses overcharging.

[0025] Below, the present invention will be described in more detail. The halftone phase-shift blank mask (halftone phase-shift type blank mask) of the present invention is a halftone formed on a transparent substrate such as a quartz substrate and is composed of a single layer or a plurality of layers (that is, two or more layers) Phase shift film. In the present invention, the transparent substrate is suitable, for example, a transparent substrate called a 6025 substrate with a thickness of 6 square inches and a thickness of 25 millimeters specified in the SEMI standard. transparent substrate. Furthermore, the halftone phase shift mask (halftone phase shift type mask) of the present invention has a mask pattern (mask pattern) of the halftone phase shift film. 1(A) is a cross-sectional view showing an example of a halftone phase-shift blank mask of the present invention. This half-tone phase-shift blank mask 100 is provided with a transparent substrate 10 and a half-tone formed on the transparent substrate 10. Hue Phase Shift Film 1. 1(B) is a cross-sectional view showing an example of the halftone phase shift mask of the present invention. The halftone phase shift mask 101 is provided with a transparent substrate 10 and a halftone phase shift mask formed on the transparent substrate 10. Membrane pattern 11. Halftone phase-shift film, although single-layer formation can meet the necessary phase difference and transmittance as halftone phase-shift film, but for example in order to satisfy predetermined surface reflectivity, and comprise the layer with anti-reflection functionality, In this way, it is also suitable to form a plurality of layers in order to satisfy the retardation and transmittance required as a halftone phase shift film as a whole. [0028] Even in the case of a single layer and a plurality of layers, each layer may be formed so that the composition of a part or all of the constituent elements changes continuously in the thickness direction. In particular, in the layer (A) having a predetermined composition, which will be described later, the composition of a part or all of the constituent elements is appropriately changed continuously in the thickness direction. Also, when the halftone phase shift film is composed of a plurality of layers, it may be a combination of two or more layers selected from a layer with different constituent elements and a layer with the same constituent element and a different composition ratio, and when the plurality of layers is composed of three or more layers, If it must be used as an adjacent layer, the same layer can also be combined. The halftone phase shift film of the present invention is in the predetermined film thickness, with respect to the light below the wavelength of 200nm, especially the ArF excimer laser light (wavelength) used in the light lithography using the halftone phase shift mask. 193 nm) exposure light to give a predetermined phase shift amount (phase difference) and a predetermined transmittance to the film. [0030] The thickness of the entire halftone phase shift film of the present invention is preferably 70 nm or less, more preferably 65 nm or less, since the thinner the film, the easier it is to form a fine pattern. On the other hand, the lower limit of the film thickness of the halftone phase shift film is set to the light having a wavelength of 200 nm or less with respect to the exposure wavelength, and is set within the range to obtain the necessary optical properties, and in particular, although there is no limitation, generally it can be 40 nm or more. . The phase difference with respect to the exposure light of the halftone phase shift film of the present invention is at the boundary between the portion where the halftone phase shift film is present (halftone phase shift portion) and the portion where the halftone phase shift film is not present. , Interfering with the exposure light by passing through the phase difference of the respective exposure light, if the phase difference of contrast can be increased, the phase difference can be 150-200°. In general halftone phase shift films, although the retardation is set at about 180°, from the viewpoint of increasing the above-mentioned contrast, the retardation is not limited to about 180°, and the retardation can be made smaller than 180°. or larger. For example, if the retardation is made smaller than 180°, it is effective for thinning. However, from the viewpoint of obtaining a higher contrast, it goes without saying that a phase difference close to 180° is effective, preferably 160-190°, more preferably 175-185°, and still more preferably about 180°. On the other hand, the transmittance to exposure light of the halftone phase shift film of the present invention is preferably 3% or more, more preferably 5% or more, and more preferably 30% or less. [0032] The halftone phase shift film of the present invention preferably has a surface roughness RMS of 0.6 nm or less. For this surface roughness RMS, for example, the surface roughness RMS measured by AFM (atomic force microscope) can be applied. The surface roughness is preferably smaller in order to detect smaller defects in defect inspection. In addition, the halftone phase shift film of the present invention preferably has a sheet resistance of 10 ¹³ Ω/□ or less, more preferably 10 ¹² Ω/□ or less, especially in the layer (A) having a predetermined composition described later, preferably The sheet resistance is 10 ¹⁵ Ω/□ or less, more preferably 10 ¹³ Ω/□ or less. When the sheet resistance of the halftone phase shift film is performed in this way, it is possible to suppress the overcharge (charge-up), for example, the size measurement of the mask pattern by an electron microscope such as SEM (Scanning Electron Microscope), etc. Overcharge, can measure more accurate size. In the halftone phase shift film of the present invention, within the range that satisfies the above-mentioned predetermined retardation, predetermined transmittance and predetermined film thickness, preferably the refractive index n with respect to the exposure light is 2.4 or more, More preferably, it is 2.5 or more, and still more preferably 2.6 or more. When reducing the oxygen content of the halftone phase shift film, it is preferable that the refractive index n of the film can be increased by not containing oxygen, and the film can be thinned in addition to securing the retardation necessary for the phase shift film thickness. The lower the refractive index n-based oxygen content is, the higher the refractive index n is, the higher the refractive index n is, the more retardation necessary for the thin film can be obtained. When the halftone phase shift film is formed as a single layer, the single layer is preferably The refractive index n is set to be 2.4 or more, more preferably 2.5 or more, and still more preferably 2.6 or more. On the other hand, when the halftone phase shift film is formed of a plurality of layers, it is preferably 60% or more of the entire film thickness, more preferably 70% or more, still more preferably 80% or more, and still more preferably 90% or more , particularly preferably 100%, and the refractive index n is set to be 2.4 or more, more preferably 2.5 or more, and still more preferably 2.6 or more. In the halftone phase shift film of the present invention, within the range that satisfies the above-mentioned predetermined retardation, predetermined transmittance and predetermined film thickness, preferably the extinction coefficient k relative to the exposure light is 0.4 or more, More preferably, it is 0.6 or more and 0.7 or less, and more preferably 0.65 or less. When the halftone phase shift film is constituted by a single layer, the single layer preferably has an extinction coefficient k of 0.4 or more, more preferably 0.6 or more, and 0.7 or less, and more preferably 0.65 or less. On the other hand, when the halftone phase shift film is constituted by a plurality of layers, it is preferably 60% or more of the entire film thickness, more preferably 70% or more, more preferably 80% or more, still more preferably 90% or more, especially It is preferably 100%, and the extinction coefficient k is set to be 0.1 or more, more preferably 0.2 or more, and 0.7 or less, and more preferably 0.65 or less. The halftone phase shift film of the present invention is composed of a silicon-based material containing transition metals, silicon and nitrogen as essential components, and may contain oxygen as an arbitrary component. The single layer or multiple layers of the halftone phase shift film are formed. Each layer is composed of a silicon-based material containing transition metal, silicon and nitrogen as essential components, and optionally oxygen as an optional component. The content of elements other than these can be tolerated as long as the amount of impurities is present. In addition, the halftone phase shift film of the present invention includes at least one layer (A) having a predetermined composition, which will be described later. When it is constituted by a single layer, when the entire single layer is constituted by a plurality of layers, when a surface oxide layer, which is described later, is provided , to remove the surface oxide layer, preferably more than 50% of the film thickness, more preferably more than 60%, still more preferably more than 70% of the layer (A) having a predetermined composition described later. The ratio of the layer (A) is further preferably 80% or more, more preferably 90% or more, and still more preferably 100% (ie, the whole). When the halftone phase shift film is constituted by a plurality of layers, it is preferable that the layer of the outermost surface portion on the side separated from the transparent substrate of the halftone phase shift film is the (A) layer. In the halftone phase shift film of the present invention, the content of the transition metal contained in the silicon-based material constituting the layer (A) is preferably 3 atomic % or less, more preferably 2 atomic % or less, and still more preferably 1.5 atomic % or less. At % or less, the transition metal is preferably contained at 0.1 at % or more, more preferably 0.5 at % or more, and still more preferably 1 at % or more. Furthermore, from the viewpoint of the sheet resistance of the halftone phase shift film, it is preferable to include the transition metal in an amount of 0.1 atomic % or more, more preferably 0.5 atomic % or more, and even more preferably 1 atomic % or more. From the viewpoint of sufficient sheet resistance, it is more preferably more than 1 atomic %, and still more preferably 1.1 atomic % or more. As the transition metal, for example, molybdenum, zirconium, tungsten, titanium, hafnium, chromium, tantalum, etc. are included, and molybdenum is especially preferred, and the transition metal is more preferably composed of molybdenum. [0037] The halftone phase shift film of the present invention is preferably the content ratio of the total of silicon, nitrogen and oxygen contained in the silicon-based material constituting the (A) layer (when oxygen is not included, the content ratio of silicon and oxygen) It is 90 atomic % or more, more preferably 95 atomic % or more. In the halftone phase shift film of the present invention, the content of silicon contained in the silicon-based material constituting the layer (A) is preferably 30 atomic % or more, more preferably 40 atomic % or more, and 70 atomic % Hereinafter, 55 atomic % or less is more preferable, and 50 atomic % or less is preferably 10% or more of the total film thickness of the (A) layer. In particular, when the halftone phase shift film has a low transmittance (for example, 3% or more and less than 20%, more preferably 3% or more and 12% or less, still more preferably 3% or more and less than 10%) , preferably the content of silicon contained in the silicon-based material is 40 atomic % or more, more preferably 44 atomic % or more, and 70 atomic % or less, more preferably 55 atomic % or less, and preferably 50 atomic % or less At least 10% of the total film thickness of the (A) layer, and the halftone phase shift film has a high transmittance (for example, 20% or more and 30% or less), preferably The content rate of silicon contained in the silicon-based material is 30 atomic % or more, more preferably 40 atomic % or more, and 55 atomic % or less, more preferably 50 atomic % or less, and preferably 45 atomic % or less. A part has 10% or more of the total film thickness of the (A) layers. In the halftone phase shift film of the present invention, the total content of nitrogen and oxygen contained in the silicon-based material constituting the layer (A) is preferably 30 atomic % or more, more preferably 45 atomic % or more, and It is 60 atomic % or less, more preferably 55 atomic % or less, and preferably 50 atomic % or more is 10% or more of the total film thickness of the (A) layer. In the halftone phase shift film of the present invention, the content of nitrogen contained in the silicon-based material constituting the layer (A) is preferably 10 atomic % or more, more preferably 40 atomic % or more, and 60 atomic % Below, it is more preferable that it is 55 atomic% or less. In particular, when the halftone phase shift film has a low transmittance (for example, 3% or more and less than 20%, more preferably 3% or more and 12% or less, still more preferably 3% or more and less than 10%) , the nitrogen content of the silicon-based material is preferably 40 atomic % or more, more preferably 44 atomic % or more, and 60 atomic % or less, more preferably 56 atomic % or less, and preferably 48 atomic % or less At % or more, more preferably 50 at % or more, the portion is 10% or more of the total film thickness of the (A) layer. In addition, when the halftone phase shift film has a high transmittance (for example, 20% or more and 30% or less), the content of nitrogen contained in the silicon-based material is preferably 10 atomic % or more, more preferably 40 atomic % % or more and 60 atomic % or less, more preferably 55 atomic % or less. [0041] In the halftone phase shift film of the present invention, the content of oxygen contained in the silicon-based material constituting the (A) layer is preferably 30 atomic % or less, more preferably 6 atomic % or less. In particular, when the halftone phase shift film has high transmittance (for example, 20% or more and 30% or less), preferably 30 atomic % or less, more preferably 25 atomic % or less, the halftone phase shift film has low transmittance In the case of the ratio (for example, 3% or more and less than 20%, more preferably 3% or more and 12% or less, still more preferably 3% or more and less than 10%), it is preferably 6 atomic % or less, more preferably Preferably it is 3.5 atomic % or less, More preferably, it is 1 atomic % or less. As the silicon-based material, transition metal silicon-based materials can be cited, specifically, transition metal-silicon-based materials composed of only transition metal (Me), silicon and nitrogen (ie, transition metal silicon nitride (MeSiN) can be cited. )), or transition metal-silicon-based materials (ie, transition metal silicon oxynitride (MeSiON)) only composed of transition metals, silicon, nitrogen and oxygen. [0043] Furthermore, in order to reduce the thickness of the halftone phase shift film, it is preferable that the content rate of oxygen is low, and it is more preferable to not contain oxygen. From this viewpoint, it is preferable to make the halftone phase shift film a silicon-based material that does not contain oxygen. The etching rate of the fluorine-based dry etching of the halftone phase-shift film of the present invention is preferably faster than the transparent substrate, preferably the etching rate of the halftone phase-shift film relative to the etching rate of the transparent substrate The ratio is 1.25 or more, more preferably 1.3 or more, and still more preferably 1.35 or more. By setting the ratio of the etching rate in this way, the workability of the film can be further improved. Although the halftone phase-shift film of the present invention can be formed by a known film forming method, it is preferably formed by a sputtering method that can easily obtain a film with excellent homogeneity, and DC sputtering, RF any method of sputtering. The target and the sputtering gas are appropriately selected depending on the layer composition or composition. As the target, a silicon target, a silicon nitride target, a target including both silicon and silicon nitride, or the like can be used. The contents of nitrogen and oxygen can be reacted by appropriately adjusting the introduction amount by using a gas containing nitrogen, a gas containing oxygen, a gas containing nitrogen and oxygen, a gas containing carbon if necessary, etc. Sexual sputtering, to adjust. As the reactive gas, nitrogen gas (N ₂ gas), oxygen gas (O ₂ gas), nitrogen oxide gas (N ₂ O gas, NO gas, NO ₂ gas) or the like can be specifically used. Furthermore, as the rare gas in the sputtering gas, helium gas, neon gas, argon gas, or the like can also be used. When the halftone phase-shift film is defined as a plurality of layers, in order to suppress the change of the film quality of the halftone phase-shift film, a surface oxide layer can be provided as the layer on the outermost surface of the surface side (side away from the transparent substrate). . The oxygen content of the surface oxide layer may be 20 atomic % or more, and may be 50 atomic % or more. As a method of forming a surface oxide layer, specifically, in addition to oxidation by atmospheric oxidation (natural oxidation), as a method of forcibly performing an oxidation treatment, a film of a silicon-based material may be subjected to ozone gas or The method of ozone water treatment, or the method of heating to above 300°C by oven heating, lamp annealing, laser heating, etc. in an oxygen-existing environment such as an oxygen gas environment. The thickness of the surface oxide layer is preferably 10 nm or less, more preferably 5 nm or less, still more preferably 3 nm or less, and usually 1 nm or more is used to obtain the effect of the oxide layer. Although the surface oxide layer can also be formed by increasing the amount of oxygen in the sputtering step, it is preferably formed by the aforementioned atmospheric oxidation or oxidation treatment in order to be a layer with fewer defects. [0047] On the halftone phase shift film of the halftone phase shift blank mask of the present invention, a second layer composed of a single layer or a plurality of layers can be arranged. Layer 2 is typically positioned adjacent to the halftone phase shift film. Specific examples of the second layer include a light-shielding film, a combination of a light-shielding film and an antireflection film, and a processing aid film used as a hard mask for patterning a halftone phase shift film. Moreover, when providing the 3rd layer mentioned later, this 2nd layer can also be utilized as a process assistance film (etching stopper film) used as an etching stopper for patterning on the third layer. As the material of the second layer, a material containing chromium is suitable. [0048] As such a halftone phase shift blank mask, specifically, the one shown in FIG. 2(A) can be cited. 2(A) is a cross-sectional view showing an example of a halftone phase shift blank mask of the present invention. The halftone phase shift blank mask 100 includes a transparent substrate 10 and a halftone phase shift mask formed on the transparent substrate 10 Film 1, and the second layer 2 formed on the halftone phase shift film 1. [0049] In the halftone phase shift blank mask of the present invention, a light-shielding film can be set as the second layer on the halftone phase shift film. Moreover, as a 2nd layer, a light-shielding film and an antireflection film may be combined and provided. By providing the second layer including the light-shielding film, the halftone phase-shift mask can be provided with an area that completely shields the exposure light. This light-shielding film and anti-reflection film can also be used as a processing aid film in etching. Although there are many reports (for example, Japanese Patent Laid-Open No. 2007-33469 (Patent Document 4), Japanese Patent Laid-Open No. 2007-233179 (Patent Document 5), etc.) on the film structure and material of the light-shielding film and the anti-reflection film, there are many reports. As a preferable film structure of a combination of a light-shielding film and an anti-reflection film, for example, a light-shielding film containing a material of chrome is provided, and an anti-reflection film containing a material of chromium is provided to reduce reflection from the light-shielding film. Both the light-shielding film and the antireflection film may be constituted by a single layer, or may be constituted by a plurality of layers. Examples of the material containing chromium for the light-shielding film or the anti-reflection film include chromium alone, chromium oxide (CrO), chromium nitride (CrN), chromium carbide (CrC), chromium oxynitride (CrON), chromium oxide carbide ( CrOC), chromium nitride carbide (CrNC), chromium oxide nitride carbide (CrONC) and other chromium compounds. When the 2nd layer is the combination of light-shielding film or light-shielding film and anti-reflection film, preferably the content rate of the chromium in the chromium compound of light-shielding film is more than 40 atomic %, more preferably more than 60 atomic %, and It is less than 100 atomic %, more preferably 99 atomic % or less, still more preferably 90 atomic % or less. The oxygen content is preferably 0 atomic % or more and 60 atomic % or less, more preferably 40 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. The nitrogen content is preferably 0 atomic % or more and 50 atomic % or less, more preferably 40 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. The carbon content is preferably 0 atomic % or more and 20 atomic % or less, more preferably 10 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. In this case, the total content of chromium, oxygen, nitrogen, and carbon is preferably 95 atomic % or more, more preferably 99 atomic % or more, and even more preferably 100 atomic %. Again, when the 2nd layer is the combination of light-shielding film and anti-reflection film, anti-reflection film is preferably chromium compound, preferably the content rate of the chromium in the chromium compound is more than 30 atom %, more preferably 35 atom % or more and 70 atomic % or less, more preferably 50 atomic % or less. The oxygen content is preferably 60 atomic % or less and 1 atomic % or more, more preferably 20 atomic % or more. The nitrogen content is preferably 50 atomic % or less, more preferably 30 atomic % or less, and 1 atomic % or more, more preferably 3 atomic % or more. The carbon content is preferably 0 atomic % or more and 20 atomic % or less, more preferably 5 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. In this case, the total content of chromium, oxygen, nitrogen, and carbon is preferably 95 atomic % or more, more preferably 99 atomic % or more, and even more preferably 100 atomic %. On the other hand, the 2nd layer is in the case where the pattern formation of the halftone phase-shift film is used as the processing aid film (etching mask film) of the hard mask, and this processing aid film is related to the halftone phase shift. A material having different film etching properties, such as a material resistant to fluorine-based dry etching suitable for etching of a material containing silicon, is preferably a material containing chromium that can be etched with a chlorine-based gas containing oxygen. Specific examples of the material containing chromium include chromium alone, chromium oxide (CrO), chromium nitride (CrN), chromium carbide (CrC), chromium oxynitride (CrON), chromium oxide carbide (CrOC), Chromium compounds such as chromium nitride carbide (CrNC), chromium oxide nitride carbide (CrONC), etc. When the second layer is a processing aid film, the content of chromium in the second layer is preferably 40 atomic % or more, more preferably 50 atomic % or more, and 100 atomic % or less, more preferably 99 atomic % % or less, more preferably 90 atomic % or less. The oxygen content is preferably 0 atomic % or more and 60 atomic % or less, more preferably 55 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. The nitrogen content is preferably 0 atomic % or more and 50 atomic % or less, more preferably 40 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. The carbon content is preferably 0 atomic % or more and 20 atomic % or less, more preferably 10 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. In this case, the total content of chromium, oxygen, nitrogen, and carbon is preferably 95 atomic % or more, more preferably 99 atomic % or more, and even more preferably 100 atomic %. [0054] When the second layer is a light-shielding film or a combination of a light-shielding film and an antireflection film, the thickness of the second layer is usually 20 to 100 nm, preferably 40 to 70 nm. Moreover, it is preferable to carry out so that the total optical density of the halftone phase shift film and the 2nd layer with respect to exposure light of wavelength 200nm or less may be 2.0 or more, more preferably 2.5 or more, and still more preferably 3.0 or more. On the other hand, when the second layer is a processing aid film, the film thickness of the second layer is usually 1 to 100 nm, preferably 2 to 50 nm. [0055] On the second layer of the halftone phase shift blank mask of the present invention, a third layer composed of a single layer or a plurality of layers can be arranged. The third layer is usually arranged adjacent to the second layer. Specific examples of the third layer include a processing aid film used as a hard mask for pattern formation on the second layer, a light-shielding film, a combination of a light-shielding film and an antireflection film, and the like. As the material of the third layer, a material containing silicon is suitable, especially a material that does not contain chromium. [0056] As such a halftone phase shift blank mask, specifically, the one shown in FIG. 2(B) can be cited. 2(B) is a cross-sectional view showing an example of a halftone phase shift blank mask of the present invention. The halftone phase shift blank mask 100 includes a transparent substrate 10 and a halftone phase shifter formed on the transparent substrate 10 The film 1, the second layer 2 formed on the halftone phase shift film 1, and the third layer 3 formed on the second layer 2. When the 2nd layer is the combination of light-shielding film or light-shielding film and anti-reflection film, or when the pattern formation of above-mentioned halftone phase-shift film is used as the processing auxiliary film of hard mask, as the 3rd layer, A processing aid film (etching mask film) that can be used as a hard mask for pattern formation on the second layer. In addition, when the 4th layer mentioned later is provided, this 3rd layer can also be utilized as a process assistance film (etch-stop layer film) used as an etch stop layer for patterning on the 4th layer. This processing aid film is a material with different etching properties from the second layer, for example, a material having resistance to chlorine-based dry etching suitable for etching of materials containing chromium, and specifically, it is preferable to use SF ₆ or CF ₄ , etc. The fluorine-based gas etched materials containing silicon. Specific examples of the material containing chromium include silicon alone, a material containing silicon, one or both of nitrogen and oxygen, a material containing silicon and a transition metal, a material containing silicon, one or both of nitrogen and oxygen, and Silicon compounds, such as transition metal materials, etc., as transition metals, molybdenum, tantalum, zirconium, etc. are mentioned. When the third layer is a processing aid film, it is preferable that the processing aid film is a silicon compound, and the content of silicon in the silicon compound is preferably 20 atomic % or more, more preferably 33 atomic % or more, and 95 atomic % or more. At % or less, more preferably 80 at % or less. The nitrogen content is preferably 0 atomic % or more and 50 atomic % or less, more preferably 30 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. The oxygen content is preferably 0 atomic % or more, more preferably 20 atomic % or more, and 70 atomic % or less, more preferably 66 atomic % or less, and when it is necessary to adjust the etching rate, preferably 1 atomic % %above. The transition metal content is preferably 0 atomic % or more and 35 atomic % or less, more preferably 20 atomic % or less, and when a transition metal is contained, preferably 1 atomic % or more. In this case, the total content of silicon, oxygen, nitrogen, and transition metal is preferably 95 atomic % or more, more preferably 99 atomic % or more, and still more preferably 100 atomic %. When the 2nd layer is light-shielding film or the combination of light-shielding film and anti-reflection film, the 3rd layer is processing auxiliary film, the film thickness of the 2nd layer is usually 20～100nm, preferably 40～70nm, the 3rd The thickness of the layer is usually 1 to 30 nm, preferably 2 to 15 nm. Moreover, it is preferable to carry out so that the total optical density of the halftone phase shift film and the 2nd layer with respect to exposure light of wavelength 200nm or less may be 2.0 or more, more preferably 2.5 or more, and still more preferably 3.0 or more. On the other hand, when the second layer is a processing aid film and the third layer is a processing aid film, the film thickness of the second layer is usually 1 to 100 nm, preferably 2 to 50 nm, and the film thickness of the third layer is usually 1 to 100 nm. 30 nm, preferably 2 to 15 nm. [0060] Also, when the second layer is a processing aid film, a light-shielding film may be provided as the third layer. Moreover, as a 3rd layer, a light-shielding film and an antireflection film may be combined and provided. In this case, the second layer is used as a processing aid film (etching mask film) in the patterning of the halftone phase shift film as a hard mask, and can also be used as an etching stopper in the patterning of the third layer. The processing aid film (etch stop layer film) is used. As an example of a processing assistance film, the film which consists of a material containing chromium as shown in Unexamined-Japanese-Patent No. 2007-241065 (patent document 6) is mentioned. The processing aid film may be composed of a single layer or a plurality of layers. Examples of the material containing chromium for the processing aid film include chromium alone, chromium oxide (CrO), chromium nitride (CrN), chromium carbide (CrC), chromium oxynitride (CrON), chromium oxide carbide (CrOC), Chromium compounds such as chromium nitride carbide (CrNC), chromium oxide nitride carbide (CrONC), etc. When the second layer is a processing aid film, the content of chromium in the second layer is preferably 40 atomic % or more, more preferably 50 atomic % or more, and 100 atomic % or less, more preferably 99 atomic % % or less, more preferably 90 atomic % or less. The oxygen content is preferably 0 atomic % or more and 60 atomic % or less, more preferably 55 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. The nitrogen content is preferably 0 atomic % or more and 50 atomic % or less, more preferably 40 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. The carbon content is preferably 0 atomic % or more and 20 atomic % or less, more preferably 10 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. In this case, the total content of chromium, oxygen, nitrogen, and carbon is preferably 95 atomic % or more, more preferably 99 atomic % or more, and even more preferably 100 atomic %. On the other hand, the light-shielding film and anti-reflection film of the 3rd layer are different materials from the 2nd layer etching characteristics, such as the chlorine-based dry etching applicable to the etching of the material comprising chromium has the material of resistance, specifically and In other words, it is preferable to be a material containing silicon that can be etched with a fluorine _- based gas such as _SF6 or CF4. Specific examples of the material containing silicon include silicon alone, a material containing silicon, one or both of nitrogen and oxygen, a material containing silicon and a transition metal, a material containing silicon, one or both of nitrogen and oxygen, Silicon compounds such as transition metal materials and the like, and examples of the transition metal include molybdenum, tantalum, zirconium, and the like. When the 3rd layer is a light-shielding film or a combination of a light-shielding film and an anti-reflection film, preferably the light-shielding film and the anti-reflection film are silicon compounds, preferably the silicon compound has a content rate of more than 10 atomic % , more preferably 30 atomic % or more and less than 100 atomic %, more preferably 95 atomic % or less. The nitrogen content is preferably 0 atomic % or more and 50 atomic % or less, more preferably 40 atomic % or less, and even more preferably 20 atomic % or less. When the etching rate needs to be adjusted, it is preferably 1. atomic % or more. The oxygen content is preferably 0 atomic % or more and 60 atomic % or less, more preferably 30 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. The transition metal content is preferably 0 atomic % or more and 35 atomic % or less, more preferably 20 atomic % or less, and when a transition metal is contained, preferably 1 atomic % or more. In this case, the total content of silicon, oxygen, nitrogen, and transition metal is preferably 95 atomic % or more, more preferably 99 atomic % or more, and still more preferably 100 atomic %. The 2nd layer is processing auxiliary film, and the 3rd layer is when the combination of light-shielding film or light-shielding film and anti-reflection film, the film thickness of the 2nd layer is usually 1～20nm, preferably 2～10nm, the 3rd The thickness of the layer is usually 20 to 100 nm, preferably 30 to 70 nm. Moreover, it is preferable that the optical density of the halftone phase shift film and the total of the second layer and the third layer with respect to exposure light with a wavelength of 200 nm or less is 2.0 or more, more preferably 2.5 or more, and still more preferably 3.0 or more. way to proceed. [0065] On the third layer of the halftone phase shift blank mask of the present invention, a fourth layer composed of a single layer or a plurality of layers can be arranged. Tier 4 is usually placed adjacent to Tier 3. Specific examples of the fourth layer include a processing aid film used as a hard mask for patterning on the third layer. As the material of the fourth layer, a material containing chromium is suitable. [0066] As such a halftone phase shift blank mask, specifically, the one shown in FIG. 2(C) can be cited. 2(C) is a cross-sectional view showing an example of a halftone phase shift blank mask of the present invention. The halftone phase shift blank mask 100 includes a transparent substrate 10 and a halftone phase shifter formed on the transparent substrate 10 The film 1, the second layer 2 formed on the halftone phase shift film 1, the third layer 3 formed on the second layer 2, and the fourth layer 4 formed on the third layer 3. When the 3rd layer is the combination of light-shielding film or light-shielding film and anti-reflection film, as the 4th layer, the pattern formation that can be arranged on the 3rd layer is used as the processing auxiliary film (etching mask film) of hard mask. ). This processing aid film is a material having different etching properties from the third layer, for example, a material having resistance to fluorine-based dry etching suitable for etching of materials containing silicon. Specifically, it is preferable to use a chlorine-based gas containing oxygen. Etched material containing chromium. Specific examples of the material containing chromium include chromium alone, chromium oxide (CrO), chromium nitride (CrN), chromium carbide (CrC), chromium oxynitride (CrON), chromium oxide carbide (CrOC), Chromium compounds such as chromium nitride carbide (CrNC), chromium oxide nitride carbide (CrONC), etc. When the fourth layer is a processing aid film, the content of chromium in the fourth layer is preferably 40 atomic % or more, more preferably 50 atomic % or more, and 100 atomic % or less, more preferably 99 atomic % % or less, more preferably 90 atomic % or less. The oxygen content is preferably 0 atomic % or more and 60 atomic % or less, more preferably 40 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. The nitrogen content is preferably 0 atomic % or more and 50 atomic % or less, more preferably 40 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. The carbon content is preferably 0 atomic % or more and 20 atomic % or less, more preferably 10 atomic % or less, and when the etching rate needs to be adjusted, preferably 1 atomic % or more. In this case, the total content of chromium, oxygen, nitrogen, and carbon is preferably 95 atomic % or more, more preferably 99 atomic % or more, and even more preferably 100 atomic %. The 2nd layer is processing auxiliary film, and the 3rd layer is the combination of light-shielding film or light-shielding film and anti-reflection film, when the 4th layer is processing auxiliary film, the film thickness of the 2nd layer is usually 1～20nm, more The thickness of the third layer is usually 20 to 100 nm, preferably 30 to 70 nm, and the thickness of the fourth layer is usually 1 to 30 nm, preferably 2 to 20 nm. Moreover, it is preferable that the optical density of the halftone phase shift film and the total of the second layer and the third layer with respect to exposure light with a wavelength of 200 nm or less is 2.0 or more, more preferably 2.5 or more, and still more preferably 3.0 or more. way to proceed. [0070] The films of the second layer and the fourth layer made of a material containing chromium can be made by using a chromium target, adding any one or more targets selected from oxygen, nitrogen and carbon to the chromium, and the like, In addition, rare gases such as Ar, He, Ne, etc. are used, according to the composition of the film to be formed, a reaction of appropriately adding a sputtering gas selected from reactive gases such as oxygen-containing gas, nitrogen-containing gas, carbon-containing gas, etc. film formation by sputtering. [0071] On the other hand, the film made of the material containing silicon of the third layer uses a silicon target, a silicon nitride target, a target containing both silicon and silicon nitride, a transition metal target, and a composite of silicon and transition metal. Targets, etc., in rare gases such as Ar, He, Ne, etc., can be appropriately added by using a reactive gas selected from the group consisting of oxygen-containing gas, nitrogen-containing gas, carbon-containing gas, etc. according to the composition of the film to be formed. The film is formed by reactive sputtering of the sputtering gas. [0072] The halftone phase shift mask of the present invention can be fabricated by conventional methods from a halftone phase shift blank mask. For example, on the halftone phase shift film, as the second layer, in forming a halftone phase shift blank mask of a film containing a material of chrome, for example, the halftone phase shift mask can be produced by the following steps. First, on the second layer of the halftone phase shift blank mask, an electron beam resist film is formed into a film, and after pattern drawing by electron beam is performed, a resist is obtained by a predetermined development operation graphic. Next, using the obtained resist pattern as an etching mask, the resist pattern is transferred to the second layer by chlorine-based dry etching containing oxygen to obtain the pattern of the second layer. Next, using the obtained pattern of the second layer as an etching mask, the pattern of the second layer is transferred to the halftone phase shift film by fluorine-based dry etching to obtain a halftone phase shift film pattern. In this case, when a part of the second layer must remain, after forming a resist pattern for protecting the part on the second layer, the chlorine-based dry etching containing oxygen is used to remove the unprotected resist pattern. part of the second layer. Furthermore, a halftone phase shift mask can be obtained by removing the resist pattern by a conventional method. Again, on the halftone phase-shift film, as the 2nd layer, form the combination of the light-shielding film comprising the material of chromium or the combination of light-shielding film and anti-reflection film, on the 2nd layer, as the 3rd layer, To form a halftone phase shift blank mask of a processing aid film of a material containing silicon, for example, the halftone phase shift mask can be produced by the following steps. First, on the third layer of the halftone phase shift blank mask, an electron beam resist film is formed into a film, and after pattern drawing by electron beam is performed, a resist film is obtained by a predetermined development operation. eclipse pattern. Next, using the obtained resist pattern as an etching mask, the resist pattern is transferred to the third layer by fluorine-based dry etching to obtain the pattern of the third layer. Next, the obtained pattern of the third layer is used as an etching mask, and the pattern of the third layer is transferred to the second layer by chlorine-based dry etching containing oxygen to obtain the pattern of the second layer. Next, after removing the resist pattern, the obtained pattern of the second layer is used as an etching mask, and the pattern of the second layer is transferred to the halftone phase shift film by fluorine-based dry etching to obtain a halftone phase shift film. Film patterning, while removing the pattern of layer 3. Next, after forming a resist pattern protecting the portion of the remaining second layer on the second layer, the second layer of the portion not protected by the resist pattern is removed by chlorine-based dry etching containing oxygen. Furthermore, a halftone phase shift mask can be obtained by removing the resist pattern by a conventional method. On the other hand, on the halftone phase shift film, as the second layer, a processing aid film containing a material of chromium is formed, and on the second layer, as a third layer, a light shielding film containing a material of silicon is formed The halftone phase shift blank mask of the film, or the combination of the light-shielding film and the anti-reflection film, for example, the halftone phase shift mask can be manufactured by the following steps. First, on the third layer of the halftone phase shift blank mask, an electron beam resist film is formed into a film, and after pattern drawing by electron beam is performed, a resist film is obtained by a predetermined development operation. eclipse pattern. Next, using the obtained resist pattern as an etching mask, the resist pattern is transferred to the third layer by fluorine-based dry etching to obtain the pattern of the third layer. Next, the obtained pattern of the third layer is used as an etching mask, and the pattern of the third layer is transferred to the second layer by chlorine-based dry etching containing oxygen to obtain a part of removing the halftone phase shift film. Pattern of layer 2 with layer 2 removed. Next, the resist pattern is removed, and a resist pattern for protecting the portion of the remaining third layer is formed on the third layer, and the obtained pattern of the second layer is used as an etching mask, and fluorine-based dry etching is performed. , transfer the pattern of the second layer to the halftone phase shift film to obtain the pattern of the halftone phase shift film, and at the same time remove the part of the third layer that is not protected by the resist pattern. Next, the resist pattern is removed by an ordinary method, and the second layer is removed from the portion where the third layer is removed by chlorine-based dry etching containing oxygen, thereby obtaining a halftone phase shift mask. Further, on the halftone phase shift film, as the second layer, a processing aid film containing a material of chromium is formed, and on the second layer, as a third layer, a light shielding film containing a material of silicon is formed, Or the combination of the light-shielding film and the anti-reflection film, and then, on the 3rd layer, as the 4th layer, form the halftone phase shift blank mask of the processing auxiliary film of the material comprising chromium, for example, the following steps can be used to manufacture the halftone phase shift blank mask. Hue phase shift mask. First, on the fourth layer of the halftone phase shift blank mask, an electron beam resist film is formed into a film, and after pattern drawing by electron beam is performed, a resist film is obtained by a predetermined development operation. eclipse pattern. Next, using the obtained resist pattern as an etching mask, the resist pattern is transferred to the fourth layer by chlorine-based dry etching containing oxygen to obtain the pattern of the fourth layer. Next, the obtained pattern of the fourth layer is used as an etching mask, and the pattern of the fourth layer is transferred to the third layer by fluorine-based dry etching to obtain the pattern of the third layer. Next, the resist pattern is removed, and a resist pattern for protecting the part of the remaining third layer is formed on the fourth layer, and the obtained third layer pattern is used as an etching mask, and the pattern of the third layer is used as an etching mask. In dry etching, the pattern of the third layer is transferred to the second layer to obtain the pattern of the second layer, and at the same time, the part of the fourth layer that is not protected by the resist pattern is removed. Secondly, the pattern of the second layer is used as an etching mask, and the pattern of the second layer is transferred to the halftone phase shift film by fluorine-based dry etching to obtain the pattern of the halftone phase shift film. The 3rd layer of the protected part of the etched pattern. Next, the resist pattern is removed by a conventional method. Furthermore, the second layer from the portion where the third layer was removed and the fourth layer from the portion where the resist pattern was removed were removed by chlorine-based dry etching containing oxygen, thereby obtaining a halftone phase shift mask. The halftone phase mask of the present invention is used to form a pattern with a half pitch of less than 50 nm, more preferably less than 30 nm, and more preferably less than 20 nm in the photolithography of the substrate to be processed. The photoresist film formed on the substrate is particularly effective for pattern transfer with exposure light with a wavelength of ₂₀₀ nm or less, such as ArF excimer laser light (wavelength 193nm), F2 laser light (wavelength 157nm). [Examples] [0081] Hereinafter, the present invention will be specifically described by showing examples and comparative examples, but the present invention is not limited to the following examples. [Example 1] With a DC magnetron sputtering apparatus capable of discharging two targets at the same time, a MoSi target and a Si target were installed, 35 W was applied to the MoSi target, and 1,900 W of electric power was applied to the Si target, and simultaneously Discharge, introduce Ar gas and N ₂ gas as sputtering gas, fix Ar gas at 21sccm, make N ₂ gas continuously change between 26 and 47sccm for sputtering, on a quartz substrate with a square of 152mm and a thickness of 6.35mm, The film is composed of MoSiN, which has a continuous gradient composition in the thickness direction, a phase difference of 179° at a wavelength of 193nm, a transmittance of 6%, and a halftone phase shift film with a film thickness of 65nm. Get a halftone phase shift blank mask. The composition of the halftone phase-shift film measured by XPS (X-ray photoelectric spectroscopy) is a composition in which the content of Mo and N in the thickness direction continuously decreases, and the content of silicon increases continuously. The transparent substrate side The composition was Mo:Si:N=1.4:46.5:52.1 (atomic ratio), and the composition on the surface side (side away from the transparent substrate) was Mo:Si:N=0.9:52.3:46.8 (atomic ratio). In addition, the thickness of the portion where the Mo content exceeds 1.1 atomic % accounts for 50% of the thickness of the entire halftone phase shift film. [0084] The surface roughness RMS measured by AFM of this halftone phase shift film is 0.51 nm, and the sheet resistance is 10 ¹² Ω/□. Furthermore, using SF ₆ gas and O ₂ gas, the etching rate of the fluorine-based dry etching was 0.76 nm/sec, which was 1.43 times the etching rate (0.53 nm/sec) of the quartz substrate under the same conditions. Fluorine-based dry etching is used in an etching device with two high-frequency power supplies. One high-frequency power supply is set as reactive ion etching for continuous discharge at 54W, and the other high-frequency power supply is set as continuous discharge at 325W. Inductively coupled plasma was carried out by setting the flow rate of SF ₆ gas at 18 sccm and the flow rate of O ₂ gas at 45 sccm. Chemical resistance is obtained by the above-mentioned method in a mixture of ammonia hydrogen peroxide (30 mass % ammonia water: 30 mass % hydrogen peroxide water: pure water=1:1:200 (volume ratio)). The halftone phase-shift film was immersed for 120 minutes for evaluation. As a result, the amount of change in the retardation after the treatment was 0° and there was no change, and the chemical resistance was good. In addition, for the halftone phase shift film obtained by the above-mentioned method, a mask pattern with a line width of 200 nm was formed by a conventional method, which was designated as a halftone phase shift mask. ℃) and the relative humidity of 45% in the atmosphere, after the pulse of ArF excimer laser is irradiated with 40kJ/ ^cm2 of cumulative exposure, the change of the line width of the mask pattern is less than 1nm, and there is almost no change. Dimensional change is good. [Comparative Example 1] By using the same sputtering apparatus as in the Example, only the Si target was installed, only the Si target was applied with an electric power of 1,900 W to discharge it, and Ar gas and N ₂ gas were introduced as the sputtering gas, The Ar gas is fixed at 22sccm, and the N ₂ gas is continuously changed between 23.5 and 44.5sccm for sputtering. On a quartz substrate of 152mm square and a thickness of 6.35mm, the film is formed of SiN, and has a composition in the thickness direction of A halftone phase shift film with a continuous change of slope composition, a phase difference of 179° at a wavelength of 193nm, a transmittance of 6%, and a film thickness of 64nm is obtained to obtain a halftone phase shift blank mask. [0087] The surface roughness RMS measured by AFM of this halftone phase shift film is 0.51 nm, and the sheet resistance is higher than the determination limit, that is, 10 ¹³ Ω/□. On the other hand, the etching rate of the halftone phase shift film evaluated by the same method as in Example 1 was 0.65 nm/sec, which was 1.23 times the etching rate of the quartz substrate. Furthermore, the chemical resistance evaluated by the same method as Example 1 is good if the amount of change in phase difference after the treatment is 0° and there is no change. In addition, the pattern size variation evaluated by the same method as in Example 1 means that the amount of change in the line width of the mask pattern is 1 nm or less, and almost no change is considered good. [Comparative Example 2] Using the same sputtering apparatus as in the Example, a MoSi target and a Si target were mounted, 725 W was applied to the MoSi target, and 1,275 W of electric power was applied to the Si target, and at the same time, it was discharged, and Ar gas and N ₂ gas and O ₂ gas were used as sputtering gas, Ar gas was fixed at 8.5 sccm, N ₂ gas was fixed at 65 sccm, and O ₂ gas was fixed at 2.6 sccm for sputtering, on a quartz substrate of 152 mm square and 6.35 mm thick The upper film is composed of MoSiON, has a constant composition in the thickness direction, the retardation of light with a wavelength of 193 nm is 177°, the transmittance is 6%, and the film thickness is 75 nm. Hue phase shift blank mask. [0089] The composition of the halftone phase shift film measured by XPS is Mo:Si:N:O=8.7:36.1:45.1:10.1 (atomic ratio). In addition, the surface roughness RMS measured by AFM of this halftone phase shift film was 0.75 nm. Furthermore, the pattern size variation evaluated by the same method as in Example 1 was degraded because the variation in the line width of the mask pattern was as large as 26.7 nm.

[0090] 1‧‧‧Halftone phase shift film 2‧‧‧Second layer 3‧‧‧3rd layer 4‧‧‧4th layer 10‧‧‧Transparent substrate 11‧‧‧Halftone phase shift film pattern 100‧‧‧Halftone Phase Shift Blank Mask101‧‧‧Halftone Phase Shift Mask

[0024] [Fig. 1] is a cross-sectional view showing an example of the halftone phase shift blank mask and the halftone phase shift mask of the present invention. Fig. 2 is a cross-sectional view showing another example of the halftone phase shift blank mask of the present invention.

1‧‧‧Halftone Phase Shift Film

10‧‧‧Transparent substrate

11‧‧‧Halftone Phase Shift Film Pattern

100‧‧‧ Halftone Phase Shift Blank Mask

101‧‧‧Halftone Phase Shift Mask

Claims (12)

A halftone phase shift blank mask, which is composed of a single layer or a plurality of layers on a transparent substrate, with a light with a wavelength below 200nm, a phase shift amount of 150~200°, and a transmittance of more than 3% and no A halftone phase shift blank mask with a full 20% halftone phase shift film, characterized in that the halftone phase shift film is a silicon-based material containing transition metals, silicon and nitrogen as essential components, and optionally oxygen as an optional component As a layer constituting the above-mentioned halftone phase shift film, at least one (A) layer is included, and the (A) layer is composed of a transition metal content of 0.1 to 1.5 atomic %, a total of silicon, nitrogen, and oxygen. Silicon-based material with a content of 98.5 to 99.9 atomic % or more, a silicon content of 38.5 to 69.9 atomic %, a total nitrogen and oxygen content of 30 to 60 atomic %, and an oxygen content of 30 atomic % or less The sheet resistance is 10 ¹³ Ω/□ or less, and the composition of a part or all of the above-mentioned (A) layer-based constituent elements changes continuously in the thickness direction. The halftone phase shift blank mask of claim 1, wherein the transition metal system comprises molybdenum. The halftone phase shift blank mask of claim 1, wherein the thickness of the phase shift film is 70 nm or less. The halftone phase shift blank mask according to any one of claims 1 to 3, wherein the surface roughness RMS of the halftone phase shift film is 0.6 nm or less. The halftone phase shift blank mask according to any one of claims 1 to 3, further comprising, on the halftone phase shift film, a second single layer or a plurality of layers of a material including chromium. Floor. The halftone phase-shift blank mask of claim 5, wherein the second layer is a light-shielding film, a combination of a light-shielding film and an anti-reflection film, or is used as a hard mask in patterning of the above-mentioned halftone phase-shift film The processing aid film. The halftone phase shift blank mask of claim 5, further comprising, on the second layer, a third layer consisting of a single layer or a plurality of layers made of a material containing silicon. The halftone phase-shift blank mask of claim 7, wherein the second layer is a light-shielding film, or a combination of a light-shielding film and an anti-reflection film, or is used as a hard mask in patterning of the above-mentioned halftone phase-shift film As a processing aid film for the mask, the third layer is used as a processing aid film for the hard mask in the pattern formation of the second layer. The halftone phase-shift blank mask of claim 7, wherein the second layer is used as a hard mask in the patterning of the halftone phase-shift film, and is used in the patterning of the third layer The third layer is a light-shielding film, or a combination of a light-shielding film and an antireflection film, as a processing aid for the etching stopper layer. The halftone phase shift blank mask of claim 7, further comprising a fourth layer consisting of a single layer or a plurality of layers made of a material including chromium on the third layer. The halftone phase shift blank mask of claim 10, wherein the second layer is used as a hard mask in the pattern formation of the halftone phase shift film, and is used in the pattern formation of the third layer As a processing aid film for the etching stop layer, the third layer is a light-shielding film or a combination of a light-shielding film and an anti-reflection film, and the fourth layer is used as a processing aid for the hard mask in the patterning of the third layer membrane. A halftone phase shift mask is characterized by using the halftone phase shift blank mask according to any one of claim 1 to 11 and formed.

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